US Geological Survey


Date of this Version



Published in Chemical Geology 215 (2005)


The stable-isotope geochemistry of sulfate minerals that form principally in I-type igneous rocks and in the various related hydrothermal systems that develop from their magmas and evolved fluids is reviewed with respect to the degree of approach to isotope equilibrium between minerals and their parental aqueous species. Examples illustrate classical stable-isotope systematics and principles of interpretation in terms of fundamental processes that occur in these systems to produce (1) sulfate in igneous apatite, (2) igneous anhydrite, (3) anhydrite in porphyry-type deposits, (4) magmatic-hydrothermal alunite and closely related barites in high-sulfidation mineral deposits, (5) coarse-banded alunite in magmatic-steam systems, (6) alunite and jarosite in steam-heated systems, (7) barite in low-sulfidation systems, (8) all of the above minerals, as well as soluble Al and Fe hydroxysulfates, in the shallow levels and surface of active stratovolcanoes. Although exceptions are easily recognized, frequently, the sulfur in these systems is derived from magmas that evolve fluids with high H2S/SO2. In such cases, the δ34S values of the igneous and hydrothermal sulfides vary much less than those of sulfate minerals that precipitate from magmas and from their evolved fluids as they interact with igneous host rocks, meteoric water, oxygen in the atmosphere, and bacteria in surface waters. Hydrogen isotopic equilibrium between alunite and water and jarosite and water is always initially attained, thus permitting reconstruction of fluid history and paleoclimates. However, complications may arise in interpretation of δD values of magmatichydrothermal alunite in high-sulfidation gold deposits because later fluids may effect a postdepositional retrograde hydrogen– isotope exchange in the OH site of the alunite. This retrograde exchange also affects the reliability of the SO4–OH oxygen– isotope fractionations in alunite for use as a geothermometer in this environment. In contrast, retrograde exchange with later fluids is not significant in the lower temperature steam-heated environment, for which SO4–OH oxygen–isotope fractionations in alunite and jarosite can be an excellent geothermometer. Sulfur isotopic disequilibrium between coexisting (but noncontemporaneous) igneous anhydrite and sulfide may occur because of loss of fluid, assimilation of country-rock sulfur during crystallization of these minerals from a magma, disequilibrium effects related to reactions between sulfur species during fluid exsolution from magma, or because of retrograde isotope exchange in the sulfides. Anhydrite and coexisting sulfide from porphyry deposits commonly closely approach sulfur–isotope equilibrium, as is indicated by the general agreement of sulfur– isotope and filling temperatures (315 to 730 °C) in quartz. The data from anhydrite and coexisting sulfides also record a

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